1,4-dimethyl-1,2,3,4-tetrahydrobenzo[b]azepin-5-one | 72551-58-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: 1,4-dimethyl-1,2,3,4-tetrahydrobenzo[b]azepin-5-one
• 英文别名: 1,2,3,4-tetrahydro-1,4-dimethyl-5H-1-benzazepin-5-one；1,4-dimethyl-1,2,3,4-tetrahydro-benz[b]azepin-5-one；1,4-Dimethyl-1,2,3,4-tetrahydro-benz[b]azepin-5-on；1,4-Dimethyl-1,2,3,4-tetrahydro-[1]benzazepin-5-one；1,4-dimethyl-3,4-dihydro-2H-1-benzazepin-5-one
• CAS: 72551-58-7
• 化学式: C₁₂H₁₅NO
• 分子量: 189.257
• InChiKey: AHRSSVLGTMDHEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  N-methyl-N-(3-methyl-3-butenyl)-2-iodoaniline 在 tris-(dibenzylideneacetone)dipalladium(0) 、 1,1'-bis(di-tertbutylphosphino)ferrocene 、 草酰氯 、 caesium carbonate 、 三乙胺 、 9-硼双环[3.3.1]壬烷 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 、 甲苯 为溶剂， 反应 45.33h， 生成 1,4-dimethyl-1,2,3,4-tetrahydrobenzo[b]azepin-5-one
  参考文献：
  名称：

  Intramolecular Pd(0)-Catalyzed Reactions of (2-Iodoanilino)-aldehydes: A Joint Experimental–Computational Study

  摘要：

  An extensive joint experimental-computational density functional theory (DFT) study has been carried out to gain insight into the factors that control the chemoselectivity (i.e., acylation vs alpha-arylation reaction) of palladium-catalyzed cyclizations of (2-iodoanilino)-aldehydes. To this end, the nature of the tethers joining the aniline nitrogen and the aldehyde moiety, different palladium precatalysts and reaction conditions (base and temperature), as well as different additives (mono- and bidendate ligands) has been explored. The adequate selection of these variables allows for the control of the selectivity of the process. Thus, (2-iodoanilino)-aldehydes generally lead to the formation of nucleophilic addition derived products when Cs2CO3/Et3N is used as base. In contrast, the use of stronger bases like (KOBu)-O-t (in the presence of PhOH) mainly forms alpha-arylation reaction products. The different reaction pathways leading to the experimentally observed reaction products have been studied by means of computational tools.

  DOI：

  10.1021/jo301924e

文献信息

• Amine-directed intramolecular hydroacylation of alkenes and alkynes
  作者：Holly D. Bendorf、Kyle E. Ruhl、Andrew J. Shurer、Jennie B. Shaffer、Tess O. Duffin、Theresa L. LaBarte、Michelle L. Maddock、Oscar W. Wheeler

  DOI：10.1016/j.tetlet.2011.12.125

  日期：2012.3

  Medium-ring heterocycles are prepared via an amine-directed, rhodium(I)-catalyzed intramolecular hydroacylation. The presence of an allyl substituent on the amine accelerates the reaction and increases product yields.

  通过胺导向的铑（I）催化的分子内加氢酰化反应制备中环杂环。胺上烯丙基取代基的存在加速了反应并提高了产物产率。
• The Synthesis of 1-Benzazepine Derivatives as Model Compounds Related to Apo-β-Erythroidine^1,2
  作者：B. D. Astill、V. Boekelheide

  DOI：10.1021/ja01620a034

  日期：1955.8
• LENNON M.; PROCTOR G. R., J. CHEM. SOC. PERKIN TRANS., 1979, 1, NO 8, 2009-2012
  作者：LENNON M.、 PROCTOR G. R.

  DOI：——

  日期：——
• US7273880B2
  申请人：——

  公开号：US7273880B2

  公开（公告）日：2007-09-25
• Intramolecular Pd(0)-Catalyzed Reactions of (2-Iodoanilino)-aldehydes: A Joint Experimental–Computational Study
  作者：Daniel Solé、Francesco Mariani、Israel Fernández、Miguel A. Sierra

  DOI：10.1021/jo301924e

  日期：2012.11.16

  An extensive joint experimental-computational density functional theory (DFT) study has been carried out to gain insight into the factors that control the chemoselectivity (i.e., acylation vs alpha-arylation reaction) of palladium-catalyzed cyclizations of (2-iodoanilino)-aldehydes. To this end, the nature of the tethers joining the aniline nitrogen and the aldehyde moiety, different palladium precatalysts and reaction conditions (base and temperature), as well as different additives (mono- and bidendate ligands) has been explored. The adequate selection of these variables allows for the control of the selectivity of the process. Thus, (2-iodoanilino)-aldehydes generally lead to the formation of nucleophilic addition derived products when Cs2CO3/Et3N is used as base. In contrast, the use of stronger bases like (KOBu)-O-t (in the presence of PhOH) mainly forms alpha-arylation reaction products. The different reaction pathways leading to the experimentally observed reaction products have been studied by means of computational tools.